CN110817871A - Preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres - Google Patents
Preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres Download PDFInfo
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Abstract
The invention relates to the technical field of preparation and application of gel microspheres, in particular to a preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres, which comprises the following steps: s1, mixing resorcinol, formaldehyde, catalyst anhydrous sodium carbonate, graphene oxide, melamine and deionized water for reaction to obtain a reaction solution; s2, adding the reaction solution into a surfactant, and stirring to obtain uniformly dispersed reddish brown emulsion; s3, carrying out sol-gel reaction on the reddish brown emulsion, then aging the reddish brown emulsion by using an acetone solution containing trifluoroacetic acid, soaking the reddish brown emulsion in acetone, and drying the mixture under normal pressure to obtain organic aerogel; s4, carbonizing to obtain graphene-based carbon aerogel microspheres; s5 obtaining spherical carbon aerogel through KOH activation; s5 by CO2Activating; the carbon aerogel microspheres prepared by the method have moderate particle size, higher bulk density and porosity, high effective specific surface area, excellent conductivity and good wettability with electrolyte.
Description
Technical Field
The invention relates to the technical field of preparation and application of gel microspheres, in particular to a preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres.
Background
With the development of science and technology and the improvement of living standards, the demand of people on energy storage devices in terms of high energy, high power and long cycle life is continuously increasing. Both lithium ion batteries and supercapacitors have disadvantages, lithium ion batteries have problems such as low power density (less than 500 W.kg < -1 >), long charging time (1-5h), poor cycle life (500-.
Under the above circumstances, in recent years, hybrid energy storage devices having characteristics and advantages of high energy density (150-. As early as 2001, Amatucci et al reported for the first time an organic-system lithium ion capacitor assembled with Activated Carbon (AC) as the positive electrode lithium titanate (Li4Ti5O12, LTO) as the negative electrode and obtained an energy density exceeding 20 Wh.kg-1. Subsequently, more and more researchers focused on the advantages of LIC and began to engage in research and development of LIC. In brief, the LIC is a novel energy storage device assembled by respectively taking a lithium ion battery material and a super capacitor electrode material as a positive electrode and a negative electrode in a mixed matching manner. Therefore, it exhibits the dual characteristics of a lithium ion battery and a supercapacitor. A lithium-ion capacitor (LIC) is used as a new energy storage device and is superior to a lithium-ion battery in power density (up to 10 kW. kg < -1 >); and the energy density (15-150 Wh.kg < -1 >) is better than that of an electrochemical capacitor, and the cycle life can reach tens of thousands of times, thereby attracting the attention of people. Since the performance of LIC mainly depends on electrode materials, developing new electrode materials or modifying existing electrode materials has become a hot content in the research direction of LIC.
Patent No. CN201910279884.1 discloses nitrogen-doped porous cellulose-based carbon aerogel, the proposal promotes the rearrangement of the carbon structure by introducing nitrogen element into the carbon skeleton, improves the stability of functional groups on the surface of the carbon material, effectively improves the wettability of the interface between the obtained material and the electrolyte, improves the electron transfer efficiency, meanwhile, the nitrogen-doped porous cellulose-based carbon aerogel has irregular honeycomb-shaped pores, the pores comprise macropores, mesopores and micropores, the macropores are used for providing more attachment sites for electrons, the mesopores provide an electron transmission path, the micropores provide an electron storage space, the pores with different pore diameters are matched with each other, the charge storage capacity of the material is improved, the method discloses that after the nitrogen-doped porous cellulose-based carbon aerogel is prepared into an electrode material, the specific capacitance can reach 160-200 F.g < -1 > when the current density is 1 A.g < -1 >.
Patent No. 201610670934.5 discloses a method for preparing nitrogen-doped carbon aerogel for lithium ion batteries. However, the effect of the graphene-doped spherical nitrogen-doped carbon aerogel on the wettability with the electrolyte is still not ideal, and the graphene-doped spherical nitrogen-doped carbon aerogel is suitable for a lithium ion capacitor, and is different from a battery system suitable for the prior art.
Disclosure of Invention
The invention provides a preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres for solving the technical problems.
The method is realized by the following technical scheme:
a preparation method of nitrogen-doped graphene-based carbon aerogel microspheres comprises the following steps:
s1, mixing resorcinol, formaldehyde, catalyst anhydrous sodium carbonate, graphene oxide, melamine and deionized water for reaction to obtain a reaction solution;
s2, adding the reaction solution into a surfactant, and stirring to obtain uniformly dispersed reddish brown emulsion;
s3, carrying out sol-gel reaction on the reddish brown emulsion, then aging for 44-48h by using an acetone solution containing trifluoroacetic acid, soaking for 48-120h by using acetone, and drying under normal pressure to obtain organic aerogel;
s4, carbonizing to obtain graphene-based carbon aerogel microspheres;
s5 obtaining spherical carbon aerogel through KOH activation;
s5 by CO2And (3) activation: heating the spherical carbon aerogel to 800-1000 ℃ at the speed of 3-5 ℃/min in the nitrogen atmosphere, and carrying out heat preservation treatment for 1 h; then introducing carbon dioxide under the condition of heat preservation for activation for 3-4h, cooling to room temperature under the protection of nitrogen after activation, and drying to obtain activated nitrogen-doped graphene-based carbon aerogel microspheres; wherein, CO2And N2The aeration rate of (1) is 100-120 ml/min.
The specific preparation method of the reaction solution comprises the following steps: stirring resorcinol, formaldehyde, catalyst anhydrous sodium carbonate and graphene oxide dispersion liquid until resorcinol and catalyst are dissolved, stirring for 30-50min in a constant-temperature oil bath at 40-60 ℃, then adding melamine and formaldehyde into the solution in a molar ratio of 1:4, stirring until the solution is clear, stirring for 30-50min in a constant-temperature oil bath at 55-65 ℃, and then adding deionized water to enable the solid content of the whole graphene-based carbon aerogel to be 40% to obtain a reaction solution.
In the step S2, the concentration of the surfactant is 1-50%, and the stirring speed is 600-800 r/min.
The specific method of the sol-gel reaction is as follows: sealing the reddish brown emulsion liquid, placing the mixture in a constant-temperature oil bath kettle at the temperature of 40-60 ℃ for reaction for 20-24h, and adjusting the temperature of the oil bath kettle to 70-90 ℃ for reaction for 3-4 d.
The carbonization method comprises the following steps: placing the organic aerogel in a tubular furnace, heating to 800-1000 ℃ at the speed of 3-5 ℃/min under the protection of inert atmosphere or vacuum condition, preserving heat, carbonizing for 3-5h, cooling to room temperature, grinding, and sieving with a 325-mesh sieve to obtain the graphene carbon aerogel composite.
And pouring out the acetone solution every 24 hours during the soaking with the acetone, and injecting the fresh acetone solution.
The KOH activation method comprises the following steps: placing the graphene-based carbon aerogel microspheres in a planetary ball mill with the rotating speed of 400r/min for ball milling for 3-4h to obtain powdery graphene-based carbon aerogel; stirring a KOH solution, slowly adding powdered graphene-based carbon aerogel in the stirring process, continuously stirring for 10-12h after the addition is finished, drying for 8-10h under the condition of 100-plus-material 110 after the uniform mixing, then placing the mixture in a tubular furnace, heating to 800-plus-material temperature at the speed of 3-5 ℃/min for 1000 ℃ under the nitrogen atmosphere, activating at constant temperature for 3-5h, cooling to room temperature, taking out and mashing, soaking in 0.8-1.2mol/L hydrochloric acid solution for 20-24h, washing to be neutral by deionized water after filtering, and drying for 1-2d under the constant temperature condition of 115-plus-material 125 ℃ after filtering to obtain a spherical carbon aerogel sample; wherein the aeration rate of the nitrogen atmosphere is 80-100 ml/min.
The molar ratio of resorcinol to formaldehyde is 2: 1.
The surfactant is prepared from the following components in a span-80: the cyclohexane is composed of 1:9 by volume.
The trifluoroacetic acid-containing acetone solution contains 3% of trifluoroacetic acid and 97% of acetone.
The mass ratio of KOH to graphene-based carbon aerogel (GA) in the KOH solution is (4-6): 1.
the nitrogen-doped graphene-based carbon aerogel microspheres prepared by the preparation method disclosed by the invention are applied to the assembly of lithium ion capacitors.
The invention also aims to provide an application method of the nitrogen-doped graphene-based carbon aerogel microspheres in the assembly of a lithium ion capacitor, which comprises the following steps:
(1) and (3) manufacturing a negative plate: mixing nitrogen-doped graphene-based carbon aerogel microspheres, conductive carbon black and polytetrafluoroethylene in a mass ratio of 8: 1: 1, adding N-dimethyl pyrrolidone, mixing for 2-3h to obtain uniform and sticky electrode active slurry, coating the electrode active slurry on a copper foil current collector by adopting a slurry scraping machine, drying for 48-72h in a vacuum drying box at the temperature of 150-;
(2) manufacturing a positive plate: mixing LiFePO4Acetylene black and polytetrafluoroethylene according to the mass ratio of 8: 1: 1, adding N-dimethyl pyrrolidone, mixing for 2-3h to obtain uniform and sticky electrode active slurry, coating the electrode active slurry on a carbon-coated aluminum foil current collector by adopting a slurry scraping machine, drying for 48-72h in a vacuum drying oven at the temperature of 150-;
(3) assembling the soft package lithium ion capacitor: under the condition of nitrogen protection, 2 electrode plates with equal mass are taken as a positive electrode and a negative electrode respectively, the diaphragm adopts a special paper fiber diaphragm for the super capacitor, the electrolyte is special organic electrolyte for the super capacitor, then the soft-package capacitor is wound, and finally the soft-package lithium ion capacitor is assembled, wherein the shape of the battery cell is designed to be square.
The type of the soft package lithium ion capacitor is 10mm in thickness, 90mm in length and 70mm in width.
Has the advantages that:
the carbon aerogel microspheres prepared by the method have moderate particle size, higher bulk density and porosity, high effective specific surface area, excellent conductivity and good wettability with electrolyte, are beneficial to improving the capacity, ionic conductivity and the like of the carbon aerogel, and can effectively improve the energy density of a lithium ion capacitor.
In the invention, resorcinol and formaldehyde firstly undergo hydroxymethyl addition reaction to generate an intermediate mixture, then melamine is added into the intermediate mixture to continue the addition reaction, and then the melamine-resorcinol-formaldehyde network gel polymer is further formed by crosslinking. Aging with acetone solution containing trifluoroacetic acid to stabilize and maintain the network structure of the gel, replacing high surface tension water solvent in the pores of the gel with low surface tension solvent, and drying under normal pressure to retain the pore structure of the gel. And the normal pressure drying has the effect of low temperature, and can keep the pore structure in the acetone evaporation process, thereby preventing the conditions of gel structure deformation or bond fracture and the like caused by high temperature and high pressure.
According to the invention, excessive surfactant containing cyclohexane and span 80 is added to form a water-in-oil solution, and the diameter of the formed spherical water-in-oil is regulated and controlled by combining the stirring rate in the stirring sol-gel reaction, so that the morphology of the finally formed carbon aerogel is controlled, the final product is spherical, and the size of the sphere is controlled.
The lithium ion capacitor prepared by the nitrogen-doped graphene-based carbon aerogel microsphere can achieve the characteristic of obtaining higher energy density without reducing power density, and the prepared lithium ion capacitor has clean appearance and no leakage. In the process of coating slurry on the lithium ion capacitor electrode plate, the carbon aerogel is spherical, compared with normal flaky carbon aerogel, the carbon aerogel realizes the accumulation of the maximum density, and can reach larger limited specific surface area under the condition that the electrode plates are the same in size, thereby realizing higher electrochemical performance.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
The assembly method of the lithium ion capacitor in the following embodiment is as follows:
(1) and (3) manufacturing a negative plate: mixing nitrogen-doped graphene-based carbon aerogel microspheres, conductive carbon black and polytetrafluoroethylene in a mass ratio of 8: 1: 1, adding N-dimethyl pyrrolidone, mixing for 2-3h to obtain uniform and sticky electrode active slurry, coating the electrode active slurry on a copper foil current collector by adopting a slurry scraping machine, drying for 48-72h in a vacuum drying box at the temperature of 150-;
(2) manufacturing a positive plate: mixing LiFePO4Acetylene black and polytetrafluoroethylene according to the mass ratio of 8: 1: 1, adding N-dimethyl pyrrolidone, mixing for 2-3h to obtain uniform and sticky electrode active slurry, coating the electrode active slurry on a carbon-coated aluminum foil current collector by adopting a slurry scraping machine, drying for 48-72h in a vacuum drying oven at the temperature of 150-;
(3) assembling the soft package lithium ion capacitor: under the condition of nitrogen protection, 2 electrode plates with equal mass are taken as a positive electrode and a negative electrode respectively, the diaphragm adopts a special paper fiber diaphragm for the super capacitor, the electrolyte is special organic electrolyte for the super capacitor, then the soft-package capacitor is wound, and finally the soft-package lithium ion capacitor is assembled, wherein the shape of the battery cell is designed to be square;
the type of the soft package lithium ion capacitor is 10mm in thickness, 90mm in length and 70mm in width.
Example 1
Firstly, respectively weighing 15g of resorcinol and 8.181g of formaldehyde, measuring 50ml of graphene oxide dispersion liquid with the concentration of 0.25mg/ml, wherein the dispersion liquid takes deionized water as a solvent, placing the three substances into a 500ml beaker, placing the beaker into a magnetic stirrer for stirring, adding 0.1443g of catalyst anhydrous sodium carbonate after resorcinol is completely dissolved, stirring the solution for 30-50min at a constant temperature of 40-60 ℃ in an oil bath, then adding 8.59g of melamine into the solution for stirring until the solution becomes clear, stirring the solution for 30-50min with the constant temperature of 60 ℃, then adding a proper amount of deionized water to ensure that the solid content of the whole graphene-based carbon aerogel becomes 40%, then adding the reaction solution into a surfactant stirring system, ensuring the concentration of the surfactant to be between 10% and 20%, and keeping the magnetic stirring for 600-800r/min, obtaining uniformly dispersed reddish brown emulsion, transferring the emulsion into a triangular flask with a plug, and sealing;
placing the sealed triangular flask with the plug into a constant-temperature oil bath pan at the temperature of 40-60 ℃ for sol-gel reaction for one day, then adjusting the temperature of the oil bath pan to 70-90 ℃, and reacting for four days; after the completion, placing the gel into an acetone solution of prepared trifluoroacetic acid, aging for three days, soaking the wet gel in acetone which is a volatile organic solvent with a small surface tension coefficient for 3-5 days, replacing fresh acetone every 24 hours so as to replace water in the wet gel, and then placing the wet gel with the replaced solvent in the air for drying at normal pressure for 3-4 days to obtain the organic aerogel with a continuous network structure;
carbonizing organic graphene oxide-based aerogel to obtain carbon aerogel, carrying out the carbonization process in a tubular furnace, heating under the protection of inert atmosphere or vacuum condition, wherein the final carbonization temperature is 950 ℃, and controlling the heating rate and the constant temperature time to be respectively: heating from room temperature to 300 deg.C at a rate of 3 deg.C/min, and holding for 60 min; heating to 600 deg.C at a rate of 1 deg.C/min, and holding for 90 min; then heating to 950 ℃ at the speed of 5 ℃/min, and keeping the temperature for 150 min; cooling to room temperature, grinding, and sieving with a 325-mesh sieve to obtain the graphene-based carbon aerogel microspheres, wherein the BET specific surface area of the obtained graphene-based carbon aerogel microspheres in an adsorption test of N2 is 1724m2(ii)/g, average pore diameter 4.86 nm;
preparing the graphene-based carbon aerogel microspheres into a lithium ion capacitor, standing for 24 hours, and then testing the electrochemical performance of the lithium ion capacitor, wherein the steps are as follows: connecting the lithium ion capacitor to a battery tester, charging to 3.8V according to 5C multiplying power constant current, then charging at 3.8V constant voltage, standing for 5min, discharging to 0.1V at constant current, repeating the steps, and testing the capacitor, wherein the charging and discharging current used in the test of the cycle performance is 15C, and the test result is as follows: the primary specific capacity of 5C is 306mAh/g, the primary efficiency of 5C is 92.5%, the capacity retention rate of 5C is 97.6%, and the circulation capacity retention rate of 15C10000 is 82.7%. The energy density of the carbon aerogel/LiFePO 4 lithium ion capacitor is 67.6Wh/kg at most, and the power density is 1504.7W/kg at most.
Example 2
Placing the graphene-based carbon aerogel microspheres prepared in the embodiment 1 in a planetary ball mill with the rotating speed of 400r/min for ball milling for 3-4h to obtain powdered graphene-based carbon aerogel, slowly adding the powdered graphene-based carbon aerogel under the condition of continuously stirring a KOH solution (the mass ratio of KOH to GA is 5) and continuously stirring for 10-12h, after uniformly mixing, transferring the mixture to a 105 ℃ drying oven for drying for 8-10h, then placing the dried graphene-based carbon aerogel microspheres in a tubular furnace, activating the graphene-based carbon aerogel microspheres at the constant temperature of 800 ℃ and 1000 ℃ under the nitrogen atmosphere (the ventilation rate is 80-100ml/min) with the heating rate of 3-5 ℃/min, cooling the mixture to the room temperature, taking out the graphene-based carbon aerogel microspheres, and then immersing the graphene-based carbon aerogel microspheres in 1mol/L hydrochloric acid solution for fully soaking for 24 h. Filtering, washing with deionized water for several times until neutral, filtering, and oven drying (constant temperature drying at 120 deg.C for 12-24 hr) to obtain spherical carbon aerogel;
the BET specific surface area of the obtained spherical carbon aerogel N2 in an adsorption test is 2149m2(ii)/g, average pore diameter 3.59 nm;
preparing the spherical carbon aerogel into a lithium ion capacitor, standing for 24 hours, and then carrying out electrochemical performance test on the lithium ion capacitor, wherein the steps are as follows: and connecting the assembled lithium ion capacitor to a battery tester, charging to 3.8V at a constant current of 5C multiplying power, then charging at a constant voltage of 3.8V, standing for 5min, discharging to 0.1V at a constant current, repeating the steps, and testing the capacitor. Wherein, the charge-discharge current used when testing the cycle performance is 15C, and the test result is: the primary specific capacity of 5C is 348mAh/g, the primary efficiency of 5C is 91.7%, the capacity retention rate of 5C is 95.7%, and the circulation capacity retention rate of 15C10000 is 83.6%. Carbon aerogel/LiFePO4The energy density of the lithium ion capacitor is 68.5Wh/kg at most, and the power density is 1498.3W/kg at most.
Example 3
Heating the spherical carbon aerogel prepared in the embodiment 2 to 800-1000 ℃ at the speed of 3-5 ℃/min in the nitrogen atmosphere, and carrying out heat preservation treatment for 1 h; then introducing carbon dioxide under the condition of heat preservation for activation for 3-4h, cooling to room temperature under the protection of nitrogen after activation, and drying to obtain activated nitrogen-doped graphene-based carbon aerogel microspheres; wherein, CO2And N2The aeration rate is 100-120 ml/min;
the BET specific surface area of the obtained activated nitrogen-doped graphene-based carbon aerogel microsphere N2 in adsorption test is 2435m2(ii)/g, average pore diameter 5.80 nm;
activated nitrogen-doped graphene-based carbon aerogel is micro-sizedPreparing the ball into a lithium ion capacitor, standing for 24 hours, and then carrying out electrochemical performance test on the lithium ion capacitor, wherein the steps are as follows: and connecting the assembled lithium ion capacitor to a battery tester, charging to 3.8V at a constant current of 5C multiplying power, then charging at a constant voltage of 3.8V, standing for 5min, discharging to 0.1V at a constant current, repeating the steps, and testing the capacitor. Wherein, the charge-discharge current used when testing the cycle performance is 15C, and the test result is: the primary specific capacity of 5C is 376mAh/g, the primary efficiency of 5C is 92.6%, the capacity retention rate of 5C is 93.9%, and the circulation capacity retention rate of 15C10000 is 84.8%; carbon aerogel/LiFePO4The energy density of the lithium ion capacitor is at most 71.2Wh/kg, and the power density is at most 1639.5W/kg.
Comparative example 1
The preparation of the nitrogen-doped carbon aerogel is prepared by referring to 'preparation of nitrogen-doped carbon aerogel and research on electrochemical properties', and specifically comprises the following steps: mixing melamine (M) and formaldehyde (F) in a molar ratio of 1: 3 mixing and adding a proper amount of distilled water, taking anhydrous sodium carbonate (C) as a reaction catalyst, and stirring at 70 ℃ until the melamine is completely dissolved. After the solution has cooled to below 30 ℃, resorcinol (R) and another portion of formaldehyde (F) are added: the molar ratio of F is 1: 2, M: r molar ratio 1.2, (M + R): the molar ratio of C is 100: 1, stirring the solution until the solution is clear, filling the solution into a 20mL ampoule bottle, sealing the ampoule bottle by using an alcohol burner, putting the ampoule bottle into a water bath at 85 ℃ until the solution forms a gel, and continuously aging the ampoule bottle for 3 days in the water bath at 85 ℃. Then taking out the hydrogel column and putting the hydrogel column into acetone solution for replacement for 2 days, and replacing the acetone once a day to form the organogel. Carrying out supercritical drying on the organic aerogel in petroleum ether for 2h (the distillation range is 30-60 ℃, the temperature is 250 ℃, and the pressure is 7MPa) to form the organic aerogel; putting the organic aerogel into a carbonization furnace, introducing nitrogen for protection, and carbonizing at the constant temperature of 800 ℃ for 2 hours to finally form nitrogen-doped carbon aerogel;
the specific surface area is calculated by adopting a Brunauer-Elett-Teller method (BET), and the pore volume of the sample is obtained by the measured adsorption and desorption isotherm, wherein the result is as follows: 121.0m2(ii)/g; the specific capacitance was 186.3F/g.
The carbon aerogel prepared by the method is spherical, the stacking density of active substances is increased, and the volume energy density is improved. The carbon aerogel is doped with nitrogen to increase the electronegativity of the carbon material, so that the carbon aerogel is more easily infiltrated by electrolyte, and the interface resistance is reduced.
Claims (9)
1. A preparation method of nitrogen-doped graphene-based carbon aerogel microspheres is characterized by comprising the following steps:
s1, mixing resorcinol, formaldehyde, catalyst anhydrous sodium carbonate, graphene oxide, melamine and deionized water for reaction to obtain a reaction solution;
s2, adding the reaction solution into a surfactant, and stirring to obtain uniformly dispersed reddish brown emulsion;
s3, carrying out sol-gel reaction on the reddish brown emulsion, then aging for 44-48h by using an acetone solution containing trifluoroacetic acid, soaking for 48-120h by using acetone, and drying under normal pressure to obtain organic aerogel;
s4, carbonizing to obtain graphene-based carbon aerogel microspheres;
s5 obtaining spherical carbon aerogel through KOH activation;
s5 by CO2And (3) activation: heating the spherical carbon aerogel to 800-1000 ℃ at the speed of 3-5 ℃/min in the nitrogen atmosphere, and carrying out heat preservation treatment for 1 h; then introducing carbon dioxide under the condition of heat preservation for activation for 3-4h, cooling to room temperature under the protection of nitrogen after activation, and drying to obtain activated nitrogen-doped graphene-based carbon aerogel microspheres; wherein, CO2And N2The aeration rate of (1) is 100-120 ml/min.
2. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the specific preparation method of the reaction solution comprises the following steps: stirring resorcinol, formaldehyde, catalyst anhydrous sodium carbonate and graphene oxide dispersion liquid until resorcinol and catalyst are dissolved, stirring for 30-50min in a constant-temperature oil bath at 40-60 ℃, then adding melamine and formaldehyde into the solution in a molar ratio of 1:4, stirring until the solution is clear, stirring for 30-50min in a constant-temperature oil bath at 55-65 ℃, and then adding deionized water to enable the solid content of the whole graphene-based carbon aerogel to be 40% to obtain a reaction solution.
3. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the concentration of the surfactant in the step S2 is 1-50%, and the stirring rate is 600-800 r/min.
4. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the specific method of the sol-gel reaction is as follows: sealing the reddish brown emulsion liquid, placing the mixture in a constant-temperature oil bath kettle at the temperature of 40-60 ℃ for reaction for 20-24h, and adjusting the temperature of the oil bath kettle to 70-90 ℃ for reaction for 3-4 d.
5. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the carbonization method comprises the following steps: placing the organic aerogel in a tubular furnace, heating to 800-1000 ℃ at the speed of 3-5 ℃/min under the protection of inert atmosphere or vacuum condition, preserving heat, carbonizing for 3-5h, cooling to room temperature, grinding, and sieving with a 325-mesh sieve to obtain the graphene carbon aerogel composite.
6. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the KOH activation method comprises the following steps: placing the graphene-based carbon aerogel microspheres in a planetary ball mill with the rotating speed of 400r/min for ball milling for 3-4h to obtain powdery graphene-based carbon aerogel; stirring a KOH solution, slowly adding powdered graphene-based carbon aerogel in the stirring process, continuously stirring for 10-12h after the addition is finished, drying for 8-10h under the condition of 100-plus-material 110 after the uniform mixing, then placing the mixture in a tubular furnace, heating to 800-plus-material temperature at the speed of 3-5 ℃/min for 1000 ℃ under the nitrogen atmosphere, activating at constant temperature for 3-5h, cooling to room temperature, taking out and mashing, soaking in 0.8-1.2mol/L hydrochloric acid solution for 20-24h, washing to be neutral by deionized water after filtering, and drying for 1-2d under the constant temperature condition of 115-plus-material 125 ℃ after filtering to obtain a spherical carbon aerogel sample; wherein the aeration rate of the nitrogen atmosphere is 80-100 ml/min.
7. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the molar ratio of resorcinol to formaldehyde is 2: 1.
8. The method for preparing nitrogen-doped graphene-based carbon aerogel microspheres according to claim 1, wherein the surfactant is prepared by mixing the following components in a span-80: the cyclohexane is composed of 1:9 by volume.
9. The nitrogen-doped graphene-based carbon aerogel microspheres as claimed in claim 1, applied to the assembly of lithium ion capacitors.
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